Bleaching composition

ABSTRACT

A bleaching composition comprises (a) hydrogen or a peroxide to produce hydrogen peroxide in its aqueous solution and (b) an organic peracid precursor having the formula (I) in which a quaternary ammonium is connected with an alkyl through an ether, an amide or an ester.    &lt;IMAGE&gt;  (I)

This application is a divisional of copending application Ser. No.07/533,354, filed on Jun. 5, 1990, now U.S. Pat. No. 5,158,700, theentire contents of which are hereby incorporated by reference.

FIELD OF INDUSTRIAL APPLICATION

The present invention relates to a bleaching agent and bleach-detergentcomposition which contain a bleach-activating agent having a cationicgroup.

PRIOR ART

Chlorine bleaching agents have the disadvantage of being limited in thekind of fiber to which they can be applied. That is, they cannot beapplied to dyed and patterned cloths. Moreover, they have their ownsmell. Because of these disadvantages, they are being rapidly replacedby oxygen bleaching agents, which include, for example, sodiumpercarbonate and sodium perborate. Despite their high bleachingperformance and stability, oxygen bleaching agents are less effectivethan chlorine bleaching agents and hence are used in combination with ableach activating agent, which includes, for example,tetraacetylethylenediamine, acetoxybenzenesulfonate,tetraacetylglycolyluryl, and glucose pentaacetate. However, their bleachactivating effect is not sufficiently high.

SUMMARY OF THE INVENTION

In their study to develop a new oxygen bleaching agent having a higherbleaching power, the present inventors found that this object isachieved with a compound which, upon reaction with hydrogen peroxide,forms an organic peracid precursor having a cationic group. (SeeJapanese Patent Laid-open No. 315666/1988)

In their continued study, the present inventors found that it ispossible to greatly improve not only bleaching power but also detergencyby using an organic peracid precursor having a quaternary ammonium groupand an alkyl group which are connected through a specific functionalgroup such as ether, amide, and ester. This finding led to the presentinvention.

Accordingly, it is an object of the present invention to provide ableaching agent and bleach-detergent composition which comprisecontaining therein:

(a) hydrogen peroxide or a peroxide which generates hydrogen peroxide inan aqueous solution, and

(b) an organic peracid precursor represented by the general formula (I)below.

The bleaching composition of the invention comprises (a) hydrogen or aperoxide to produce hydrogen peroxide in its aqueous solution and (b) anorganic peracid precursor having the below shown formula (I) in which aquaternary ammonium is connected with an alkyl through an ether, anamide, an ester or another.

It is preferable that the organic peracid precursor is selected from thegroup consisting of the below shown (a) to (h). A mole ratio of (a) to(b) preferably ranges from 99.9/0.1 to 20/80. The composition mayfurther contain one or more selected from a surfactant, a divalent metalion sequestering agent, an alkaline agent, an inorganic electrolyte, ananti-redeposition agent, an enzyme, a fluorescent whitening agent, astabilizer for the peroxide, a perfume and a coloring agent. ##STR2##where R₁ denotes a straight-chain or branched-chain C₁ -C₂₀ alkyl oralkenyl group which may have a substituent group, an unsubstituted or C₁-C₂₀ alkyl-substituted aryl group, or an alkoxylated hydrocarbyl group;

X denotes any one of ##STR3##

Y denotes any one of ##STR4## (where n is an integer of 1 to 10)

R₂ and R₃ each denotes a C₁ -C₃ alkyl group which may have a substituentgroup,

R₄ and R₅ each denotes a C₁ -C₁₂ alkylene group which may have asubstituent group, or any one of ##STR5##

L denotes a leaving group represented by any one of ##STR6## (where R₆and R₉ each denotes an alkyl group, R₇ and R₈ each denotes hydrogen oran alkyl group, and M⁺ denotes an alkali metal ion or hydrogen ion) or aglycerin residue or sugar residue, and X⁻ denotes an inorganic ororganic counter ion, provided that when L denotes ##STR7## X⁻ does notexist.

Preferred organic peracid precursors are those in which R₁ denotes aC₁₋₁₄ (particularly C₆₋₁₂) alkyl group, R₂ and R₃ each denotes a C₁₋₂alkyl group, R₄ and R₅ each denotes a C₁₋₁₀ (particularly C₁₋₅) alkylenegroup, R₆ to R₉ each denotes a C₁₋₂ alkyl group, and n is an integer of1 to 5. Examples of X⁻ include a halogen ion, hydroxyl ion, metosulfateion, ethyl sulfate ion, sulfate ion, and acetate ion.

Examples of the organic peracid precursor (b) suitable for use in thepresent invention include those which are represented by the formulas(a) to (h)below. ##STR8## where R₁ is defined as above; m and l eachdenotes an integer of 1 to 10; and M⁺ and X⁻ may be absent in somecases.

The bleaching agent and bleach-detergent composition of the presentinvention contain a peroxide which generates hydrogen peroxide in anaqueous solution. Examples of the peroxide include sodium percarbonate,sodium tripolyphosphate-hydrogen peroxide adduct, sodiumpyrophosphate-hydrogen peroxide adduct, urea-hydrogen peroxide adduct,4Na₂ SO₄.2H₂ O₂.NaCl, sodium perborate monohydrate, sodium perboratetetrahydrate, sodium peroxide, and calcium peroxide. Preferable amongthem are sodium percarbonate, sodium perborate monohydrate, and sodiumperborate tetrahydrate.

According to the present invention, the bleaching agent andbleach-detergent composition should contain the peroxide (a) and theorganic peracid precursor (b) in a molar ratio (a)/(b) of 99.9/0.1 to20/80, preferably 99/1 to 50/50.

The bleaching agent and bleach-detergent composition of the presentinvention may contain, in addition to the essential ingredients, thefollowing components which are commonly added to bleaching agents andbleach-detergent compositions.

Surface active agents

(1) Straight-chain or branched-chain alkylbenzenesulfonate whichcontains an alkyl group having 10-16 carbon atoms on average.

(2) Alkyl or alkenyl ether sulfate to which is added 0.5-8 mol (onaverage in one molecule) of ethylene oxide, propylene oxide, butyleneoxide, ethylene oxide-propylene oxide (0.1/9.9-9.9/0.1), or ethyleneoxide-butylene oxide (0.1/9.9-9.9/0.1), with the alkyl or alkenyl groupbeing a straight-chain or branched-chain one having 10-20 carbon atomson average.

(3) Alkyl or alkenyl sulfate which contains an alkyl or alkenyl grouphaving 10-20 carbon atoms on average.

(4) Olefin sulfonate which contains 10-20 carbon atoms (on average) inone molecule.

(5) Alkane sulfonate which contains 10-20 carbon atoms (on average) inone molecule.

(6) Saturated or unsaturated fatty acid salt which contains 10-24 carbonatoms (on average) in one molecule.

(7) Alkyl or alkenyl ether carboxylate to which is added 0.5-8 mol (onaverage in one molecule) of ethylene oxide, propylene oxide, butyleneoxide, ethylene oxide-propylene oxide (0.1/9.9-9.9/0.1), or ethyleneoxide-butylene oxide (0.1/9.9-9.9/0.1), with the alkyl or alkenyl grouphaving 10-20 carbon atoms on average.

(8) A salt or ester of an α-sulfofatty acid represented by the formulabelow. ##STR9## where Y denotes a C₁ -C₃ alkyl group or counter ion, Zdenotes a counter ion, and R denotes a C₁₀ -C₂₀ alkyl or alkenyl group.The counter ion of anionic surface active agents is an alkali metal ionsuch as sodium and potassium.

(9) Polyoxyethylene alkyl or alkenyl ether to which is added 1-30 mol ofethylene oxide, with the alkyl or alkenyl group having 10-20 carbonatoms on average.

(10) Polyoxyethylene alkylphenyl ether to which is added 1-25 mol ofethylene oxide, with the alkyl group having 6-12 carbon atoms onaverage.

(11) Polyoxypropylene alkyl or alkenyl ether to which is added 1-20 molof propylene oxide, with the alkyl or alkenyl group having 10-20 carbonatoms on average.

(12) Polyoxybutylene alkyl or alkenyl ether to which is added 1-20 molof butylene oxide, with the alkyl or alkenyl group having 10-20 carbonatoms on average.

(13) Nonionic surface active agent to which is added 1-30 mol (in total)of ethylene oxide and propylene oxide, or ethylene oxide and butyleneoxide (with the ratio of ethylene oxide to propylene oxide or butyleneoxide being 0.1/9.9 to 9.9/0.1), with the alkyl or alkenyl group having10-20 carbon atoms on average.

(14) Higher fatty acid alkanolamide or alkylene oxide adduct thereofrepresented by the following general formula. ##STR10## (where R₁₁denotes a C₁₀₋₂₀ alkyl or alkenyl group, R'₁₂ denotes H or CH₃, n₃denotes an integer of 1-3, and m₃ denotes an integer of 0-3.)

(15) Sugar fatty acid ester composed of a fatty acid (having 10-20carbon atoms on average) and sucrose.

(16) Sugar fatty acid glycerin monoester composed of a fatty acid(having 10-20 carbon atoms on average) and glycerin.

(17) Alkylamine oxide represented by the general formula below.##STR11## (where R'₁₃ denotes a C₁₀₋₂₀ alkyl or alkenyl group, and R'₁₄and R'₁₅ each denotes a C₁₋₃ alkyl group.)

(18) Nonionic surface active agent available under a trade name of"Pluronic", which is obtained by the condensation of ethylene oxide.

(19) Cationic surface active agent represented by the general formulasbelow. ##STR12## (where at least one of R'₁, R'₂, R'₃, and R'₄ is aC₈₋₂₄ alkyl or alkenyl group, with the remainder being C₁₋₅ alkylgroups, and X' denotes a halogen or metosulfate.) ##STR13## (where R'₁,R'₂, R'₃, and X' are defined as above.) ##STR14## (where R'₁, R'₂, andX' are defined as above, R'₅ denotes a C₂₋₃ alkylene group, and n₄denotes an integer of 1-20.)

Divalent Metal Ion Sequestering Agent (or Builder)

One or more than one kind selected from the following alkali metal saltsand alkanolamine salts, in an amount of 0-50 wt %.

(1) Phosphates such as orthophosphate, pyrophosphate, tripolyphosphate,metaphosphate, hexametaphosphate, and salts of phytic acid.

(2) Salts of phosphonic acid such as ethane-1,1-di-phosphonic acid,ethane-1,1,2-triphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid(and derivatives thereof), ethanehydroxy-1,1,2-triphosphonic acid,ethane-1,2-dicarboxy-1,2-diphosphonic acid, and methanehydroxyphosphonicacid.

(3) Salts of phosphonocarboxylic acid such as2-phosphonobutane-1,2-dicarboxylic acid,1-phosphonobutane-2,3,4-tricarboxylic acid, andα-methylphosphonosuccinic acid.

(4) Salts of amino acid such as aspartic acid, glutamic acid, andglycine.

(5) Salts of aminopolyacetic acid such as nitrilotriacetate,iminodiacetate, ethylenediaminetetraacetate,diethylenetriaminepentaacetate, glycoletherdiaminetetraacetate,hydroxyethyliminodiacetate, triethylenetetraminehexaacetate, anddjenkolate.

(6) Polymeric electrolytes such as polyacrylic acid, polyfumaric acid,polymaleic acid, poly-α-hydroxyacrylic acid, polyacetalcarboxylic acid,and salts thereof.

(7) Alkali metal salts of organic acids such as diglycolic acid,oxydisuccinic acid, carboxymethyloxysuccinic acid, citric acid, lacticacid, tartaric acid, oxalic acid, malic acid, oxydisuccinic acid,gluconic acid, carboxymethylsuccinic acid, and carboxymethyltartaricacid.

(8) aluminosilicate represented by zeolite A.

Alkaline Agents or Inorganic Electrolytes

Silicates, carbonates, and sulfates. (Alkali metal salts arepreferable.)

Anti-Redeposition Agent

Polyethylene glycol, polyvinyl alcohol, polyvinyl pyrrolidone, andcarboxy methyl cellulose.

Enzymes

Protease, lipase, amylase, and cellulase.

Fluorescent Whitening Agent

4,4'-bis-(2-sulfostyryl)-biphenyl salt,4,4'-bis-(4-chloro-3-sulfostyryl)-biphenyl salt,2-(stilphenyl)naphthothiazole derivative, 4,4'-bis(triazol-2-yl)stilbenederivative, and bis(triazinylamino)stilbene disulfonic acid derivative.

Stabilizer for Peroxide

Magnesium salts (such as magnesium sulfate, magnesium silicate,magnesium chloride, magnesium silicofluoride, magnesium oxide, andmagnesium hydroxide), and silicates (such as sodium silicate).

Perfume and Coloring Agent Effect of the Invention

The bleaching agent and detergent of the present invention produce notonly an outstanding bleaching effect but also an outstanding cleaningeffect for sebaceous dirt and mud dirt.

The bleaching agent and bleach-detergent composition of the presentinvention contain a biodegradable bleach activating agent which ishighly safe for the human body.

EXAMPLES

The invention will be described in more detail with reference to thefollowing examples, which are not intended to restrict the scope of theinvention.

Preparation of Organic Peracid Precursor REFERENTIAL EXAMPLE 1

Synthesis of an organic peracid precursor (I-a) represented by theformula below. ##STR15##

(1) In 300 g of dimethylformaldehyde (DMF) was dispersed 100 g (0.46mol) of sodium p-phenolsulfonate which had previously been dehydrated.To the dispersion was added dropwise 64.6 g (0.46 mol) of4-chlorobutyric acid chloride at 50° C. over 30 minutes, while stirringwith a mechanical stirrer. Reaction was continued for 3 hours. DMF wasdistilled away under reduced pressure (0.5-1 mmHg) at 100° C. Theresidue waswashed with acetone. Thus there was obtained 153.5 g (80.8%purity) of an ester compound (II) represented by the formula below.(Yield:90%) ##STR16##

(2) A mixture consisting of 50 g (0.49 mol) ofN,N-dimethylpropylenediamineand 64.1 g (0.44 mol) of n-caprylic acid washeated from 100° C. to 160° C. over 11 hours during which reaction wascarried out while removing water evolved under a nitrogen stream. Thereaction product was distilled at 120°-140° C. under a reduced pressureof 0.45 mmHg. Thus there was obtained 95.8 g (95% purity) of a clearliquid amine compound (III) represented by the formula below.(Yield:92.2%) ##STR17##

(3) In 150 g of DMF were suspended 50 g (0.21 mol, 95% purity) of theaminecompound (III) and 61.7 g (0.2 mol, 80.8% purity) of the estercompound (II). They were reacted at 120° C. for 12-14 hours. Thereaction product was filtered off, and the filtrate was distilled at100° C.under a reduced pressure of 0.5-1 mmHg to remove the solvent. Theresidue was washed with acetone. Thus there was obtained 87.0 g (90%purity) of the organic peracid precursor (I-a), in the form of whitepowder, represented by the formula below. (Yield:80%) ##STR18##

REFERENTIAL EXAMPLE 2

Synthesis of an organic peracid precursor (I-b) represented by theformula below. ##STR19##

(1) A mixture consisting of 150 g (1.68 mol) ofN,N-dimethylmonoethanolamine and 31.5 g (0.56 mol) of potassiumhydroxide was heated at 105°-130° C. for reaction for 3 hours, whileremoving water evolved under a nitrogen stream. To the reaction mixturewas added dropwise 67.7 g (0.56 mol) of 1-chlorohexane at 60°-70° C.over 1 hour, followed by reaction for 3 hours. The reaction mixture wasfiltered off to remove salts and the filtrate wasdistilled at 70°-75° C.under a reduced pressure of 1 mmHg. Thus there was obtained 45.6 g (96%purity) of a clear liquid amine compound (IV) represented by the formulabelow. (Yield:45%) ##STR20##

(2) The ester compound (II) obtained in Referential Example 1 wasreacted with the amine compound (IV) just mentioned above in the samemanner as inReferential Example 1. Thus there was obtained the organicperacid precursor (I-b) represented by the formula below. (Yield:75%)##STR21##

REFERENTIAL EXAMPLE 3

Synthesis of an organic peracid precursor (I-c) represented by theformula below. ##STR22##

(1) In 150 ml of acetone was dissolved 50 g (0.49 mol) of N,N-dimethylpropylenediamine. To the solution (cooled in a water bath) wasadded dropwise 79.6 g (0.49 mol) of 2-ehtylhexanoic acid chloride over 1hour, followed by reaction for 3 hours. The reaction mixture wasneutralized with 94.4 g of 28% sodium methoxide, followed by filtrationtoremove salts. The filtrate was freed of acetone and methanol bydistillation. The residue was distilled at 145°-150° C. under a reducedpressure of 10.5 mmHg. Thus there was obtained 91.3 g (93%purity) of aclear liquid amine compound (V) represented by the formula below.

(Yield:76%) ##STR23##

(2) The ester compound (II) obtained in Referential Example 1 wasreacted with the amine compound (V) just mentioned above in the samemanner as in Referential Example 1. Thus there was obtained the organicperacid precursor (I-c) represented by the formula below.

(Yield:76%) ##STR24##

EXAMPLE 1

Bleaching agent compositions pertaining to the present invention wereprepared according to the formulation shown in Table 1. Each compositioncontains any one of the activating agents I-a, I-b, and I-c prepared inReferential Examples and the activating agents represented by theformulasbelow. For comparison, bleaching agent compositions containingno activating agents were also prepared. They were examined for thebleachingeffect. ##STR25##

Measurement of Bleaching Effect

In 300 ml of water (20° C.) were dissolved sodium percarbonate (in anamount sufficient to give 0.05% of effective oxygen) and an activatingagent (I-a to I-g) or tetraacetylethylenediamine (TAED) for comparison(inan amount of 1/16 equivalent of hydrogen peroxide in the solution).The ratio of the two components is shown in Table 1.

In the thus prepared solution were soaked five pieces of cloth stainedwithblack tea for 30 minutes. After bleaching, they were rinsed anddried, and the bleaching ratio was calculated according to the followingformula. ##EQU1##where A:reflectance of stained cloth after bleaching

B:reflectance of stained cloth before bleaching

C:reflectance of unstained cloth

Reflectance was measured by means of NDR 1001DP (with a 460 nm filter)madeby Nippon Denshoku Kogyo Co., Ltd.

The cloth stained with black tea was prepared in the following manner.First, 80 g of black tea ("Nitto Kocha" yellow package) was steeped in 3liters of boiling water (deionized) for about 15 minutes. Then, thepercolate was filtered through a piece of desized bleached cotton cloth.In the filtrate was boiled a piece of cotton shirting #2003 for about 15minutes, followed by standing for about 2 hours. The cloth was air-driedand rinsed repeatedly until the washings were clear. Finally, the clothwas dehydrated and pressed and cut into pieces, measuring 8 cm by 8 cm,for experiments.

The results of the bleaching test are shown in Table 1.

                                      TABLE 1                                     __________________________________________________________________________               Examples                    Comparative Products                   Components (wt %)                                                                        1   2   3   4   5   6   7   1   2   3   4                          __________________________________________________________________________    Sodium percarbonate                                                                      80  82  80  78  81  79  79  94  100 83  81                         1-a        20                                                                 1-b            18                                                             1-c                20                                                         1-d                    22                                                     1-e                        19                                                 1-f                            21                                             1-g                                21                                         TAED                                    6       .sup. 17*.sup.1                                                                   .sup. 19*.sup.2           Bleaching ratio (%)                                                                        41.5                                                                              42.1                                                                              41.6                                                                              40.5                                                                              41.9                                                                              40.3                                                                              41.0                                                                              22.5                                                                              14.5                                                                              40.3                                                                              37.4                     __________________________________________________________________________    *.sup.1 TAED was replaced by a compound of the formula below.                  ##STR26##                                                                    *.sup.2 TAED was replaced by a compound of the formula below.                  ##STR27##                                                                

EXAMPLE 2

In a cleaning solution containing 0.0833% of commercial heavy-dutydetergent and 0.0083% of sodium percarbonate was dissolved 0.0043% eachofI-a to I-g and TAED.

The cleaning solution was used to wash five pieces of cloth (8 cm by 8cm) stained with black tea (the same cloth as used in Example 1) in aterg-o-tometer (100 rpm) at 20° C. for 10 minutes. After rinsing anddrying, the cloth was examined for bleaching ratio in the same manner asin Example 1.

The cleaning solution was also used in the same manner as above to washfive pieces of cloth soiled with mud dirt and five pieces of clothsoiled with sebaceous dirt. The washed cloth was tested for reflectanceand the detergent efficiency was evaluated in the following manner.

Artificially Soiled Cloth (With Mud)

A piece of shirting #2023 was dipped in 1000 ml of perchloroethylenecontaining dispersed therein 150 g of Kanuma red soil (for horticulture)which had been dried at 120±5° C. for 4 hours, crushed, screenedthrougha 150-mesh (100 μm) sieve, and dried again at 120±5° C. for 2 hours.After dipping, the shirting was brushed to remove excess soil. (SeeJapanese Patent Laid-open No. 26473/1980.)

Artificially Soiled Cloth (With Sebaceous Dirt)

A piece of cotton cloth (10 cm by 10 cm) was uniformly smeared with 2 gof artificial sebaceous dirt of the following composition.

    ______________________________________                                        Cotton seed oil     60%                                                       Cholesterol         10%                                                       Oleic acid          10%                                                       Palmitic acid       10%                                                       Liquid and solid paraffins                                                                        10%                                                       ______________________________________                                    

Measurement of Reflectance

Reflectance was measured by means of NDR 1001DP made by Nippon DenshokuKogyo Co., Ltd. (with a 460 nm filter for cloth soiled with mud and a550 nm filter for cloth soiled with sebaceous dirt).

The washing efficiency was calculated according to the followingformula. ##EQU2##where A:reflectance of soiled cloth after bleaching

B:reflectance of soiled cloth before bleaching

C:reflectance of unsoiled cloth

The results of the washing test are shown in Table 2.

                                      TABLE 2                                     __________________________________________________________________________                Examples                    Comparative Products                  Activating agent                                                                          1-a 1-b 1-c 1-d 1-e 1-f 1-g TAED                                                                              1*.sup.3                                                                          2*.sup.4                                                                          3*.sup.5                  __________________________________________________________________________    Bleaching ratio (%)                                                                         12.3                                                                              13.1                                                                              11.6                                                                              10.9                                                                              13.2                                                                              12.5                                                                              12.3                                                                              1.1                                                                               0.2                                                                               11.8                                                                              11.0                    Washing efficiency (%)                                                        Cloth soiled with                                                                         75  74  74  76  75  74  75  68  70  69  67                        sebaceous dirt                                                                Cloth soiled with mud                                                                     70  69  71  70  69  71  71  62  63  63  63                        __________________________________________________________________________    *.sup.3 No activating agent was used.                                         *.sup.4 A compound of the formula below was used as the activating agent.      ##STR28##                                                                    *.sup.5 A compound of the formula below was used as the activating agent.      ##STR29##                                                                

EXAMPLE 3

Bleach-detergent compositions of the present invention, each containinga different amount of phosphorus, were prepared according to thefollowing formulations. They all exhibited good bleaching performanceand detergency.

    ______________________________________                                        (1) Phosphorus-free formulation                                               ______________________________________                                        Sodium linear dodecylbenzenesulfonate                                                                     14 wt %                                           Polyoxyethylene alkyl ether (C.sub.12 -C.sub.13, EO = 10                                                  6 wt %                                            Sodium salt of hardened tallow fatty acid                                                                 2 wt %                                            Sodium silicate No. 2       5 wt %                                            Sodium carbonate            10 wt %                                           Zeolite, type 4A            25 wt %                                           Sodium sulfate              balance                                           Bleach activating agent (I-a)                                                                             10 wt %                                           Polyethylene glycol (Mw = 6000)                                                                           2 wt %                                            Protease                    2 wt %                                            Water                       4 wt %                                            ______________________________________                                    

    ______________________________________                                        (2) Low-phosphorus formulation                                                ______________________________________                                        Sodium linear dodecylbenzenesulfonate                                                                     10 wt %                                           Sodium dodecyl sulfate      2 wt %                                            Polyoxyethylene alkyl ether (C.sub.12 -C.sub.13, EO = 7.7                                                 8 wt %                                            Sodium salt of hardened tallow fatty acid                                                                 2 wt %                                            Sodium silicate No. 1       5 wt %                                            Sodium carbonate            10 wt %                                           Zeolite, type 4A            20 wt %                                           Sodium pyrosulfate          15 wt %                                           Sodium sulfate              balance                                           Sodium perborate            10 wt %                                           Bleach activating agent (I-b)                                                                             5 wt %                                            Polyethylene glycol (Mw = 11000)                                                                          1 wt %                                            Sodium sulfite              1 wt %                                            Protease                    2 wt %                                            Water                       4 wt %                                            ______________________________________                                    

    ______________________________________                                        (3) High-phosphorus formulation                                               ______________________________________                                        Polyoxyethylene alkyl ether                                                                             20 wt %                                             (R: tallow alcohol, EO = 8.6 mol)                                             Sodium salt of hardened tallow fatty acid                                                               2 wt %                                              Sodium tripolyphosphate   30 wt %                                             Sodium perborate          10 wt %                                             Bleach activating agent (I-c)                                                                           5 wt %                                              Sodium silicate No. 2     5 wt %                                              Sodium carbonate          10 wt %                                             Sodium sulfite            1 wt %                                              Polyethylene glycol (Mw = 6000)                                                                         2 wt %                                              Protease                  2 wt %                                              Water                     6 wt %                                              Sodium sulfate            balance                                             ______________________________________                                    

We claim:
 1. A bleaching composition which comprises (a) a peroxygencompound capable of yielding hydrogen peroxide in an aqueous solutionand (b) an organic peracid precursor having the formula (I): ##STR30##where R₁ is selected from the group consisting of a straight-chain orbranched-chain C₁ -C₂₀ alkyl or alkenyl group which may have asubstituent group and, an unsubstituted or C₁ -C₂₀ alkyl-substitutedaryl group; X is selected from the group consisting of ##STR31## Y isselected from the group consisting of ##STR32## where n is an integer of1 to 10,R₂ and R₃ each is selected from the group consisting of a C₁ -C₃alkyl group which may have a substituent group, R₄ and R₅ each isselected from the group consisting of a C₁ -C₁₂ alkylene group which mayhave a substituent group, ##STR33## L is a leaving group selected fromthe group consisting of ##STR34## where R₆ and R₉ each is a alkyl group,R₇ and R₈ each is selected from the group consisting of hydrogen or analkyl group, and M⁺ denotes an alkali metal ion or hydrogen ion or aglycerin residue or sugar residue, and X is selected from the groupconsisting of an inorganic or organic counter ion, provided that when Lis selected from the group consisting of ##STR35## X⁻ does not exist. 2.The composition as claimed in claim 1, in which a mole ratio of (a) to(b) ranges from 99.9/0.1 to 20/80.
 3. The composition as claimed inclaim 1, which further contains one or more agents selected from thegroup consisting of a surfactant, a divalent metal ion sequesteringagent, an alkaline agent, an inorganic electrolyte, an anti-redepositionagent, an enzyme, a fluorescent whitening agent, a stabilizer for theperoxide, a perfume and a coloring agent.
 4. The composition claimed inclaim 1, in which said organic peracid precursor is selected from thegroup consisting of ##STR36## wherein R₁ is defined as above; and m andl denote an integer of 1 to
 10. 5. A bleaching composition whichcomprises (a) a peroxygen compound capable of yielding hydrogen peroxidein an aqueous solution and (b) an organic peracid precursor having theformula (I): ##STR37## where R₁ is selected from the group consisting ofa straight-chain or branched-chain C₁ -C₂₀ alkyl or alkenyl group whichmay have a substituent group, an unsubstituted or C₁ -C₂₀alkyl-substituted aryl group;X is ##STR38## Y is selected from the groupconsisting of ##STR39## where n is an integer of 1 to 10, R₂ and R₃ eachis selected from the group consisting of a C₁ -C₃ alkyl group which mayhave a substituent group, R₄ and R₅ each is selected from the groupconsisting of a C₁ -C₁₂ alkylene group which may have a substituentgroup, ##STR40## L is a leaving group selected from the group consistingof ##STR41## where R₆ and R₉ each is an alkyl group, R₇ and R₈ each isselected from the group consisting of hydrogen or an alkyl group, and M⁺denotes an alkali metal ion or hydrogen ion or a glycerin residue orsugar residue, and X is selected from the group consisting of aninorganic or organic counter ion, provided that when L is selected fromthe group consisting of ##STR42## X⁻ does not exist.
 6. The compositionas claimed in claim 5, in which a mole ratio of (a) to (b) is in therange of from 99.9/0.1 to 20/80.
 7. The composition as claimed in claim5, which further contains additional additives selected from the groupconsisting of a surfactant, a divalent metal ion sequestering agent, analkaline agent, an inorganic electrolyte, an anti-redeposition agent, anenzyme, a fluorescent whitening agent, a stabilizer for the peroxide, aperfume and a coloring agent.
 8. A bleaching composition which comprises(a) a peroxygen compound capable of yielding hydrogen peroxide in anaqueous solution and (b) an organic peracid precursor having the formula(I): ##STR43## where R₁ is selected from the group consisting of astraight-chain or branched-chain C₁ -C₂₀ alkyl or alkenyl group whichmay have a substituent group, and an unsubstituted or C₁ -C₂₀alkyl-substituted aryl group, X is

    --O--

Y is R₅ R₄ and R₅ and R₃ each is selected from the group consisting of aC₁ -C₃ alkyl group which may have a substituent group, R₅ is selectedfrom the group consisting of a C₁ -C₁₂ alkylene group which may have asubstituent group, ##STR44## L is a leaving group selected from thegroup consisting of ##STR45## where R₆ and R₉ each is an alkyl group, R₇and R₈ each is selected from the group consisting of hydrogen or analkyl group, and M⁺ denotes an alkali metal ion or hydrogen ion or aglycerin residue or sugar residue, and X is selected from the groupconsisting of an inorganic or organic counter ion, provided that when Lis selected from the group consisting of ##STR46## X⁻ does not exist. 9.The composition as claimed in claim 8, in which a mold ratio of (a) to(b) ranges from 99.9/0.1 to 20/80.
 10. The composition as claimed inclaim 8, which further contains one or more agents selected from thegroup consisting of a surfactant, a divalent metal ion sequesteringagent, an alkaline agent, an inorganic electrolyte, an anti-redepositionagent, an enzyme, a fluorescent whitening agent, a stabilizer for theperoxide, a perfume and a coloring agent.
 11. The composition claimed inclaim 8, in which said organic peracid precursor is selected from thegroup consisting of ##STR47## wherein R₁ is defined as above; and m andl each denote an integer of 1 to
 10. 12. A bleaching composition whichcomprises (a) a peroxygen compound capable of yielding hydrogen peroxidein an aqueous solution and (b) an organic peracid precursor having theformula (I): ##STR48## where R₁ is selected from the group consisting ofa straight-chain or branched-chain C₁ -C₂₀ alkyl or alkenyl group whichmay have a substituent group, and an unsubstituted or C₁ -C₂₀alkyl-substituted aryl group, X is ##STR49## Y is R₅ R₂ and R₃ each isselected from the group consisting of a C₁ -C₃ alkyl group which mayhave a substituent group,R₄ and R₅ each is selected from the groupconsisting of a C₁ -C₁₂ alkylene group which may have a substituentgroup, ##STR50## L is a leaving group selected from the group consistingof ##STR51## where R₆ and R₉ each is an alkyl group, R₇ and R₈ each isselected from the group consisting of hydrogen or an alkyl group, and M⁺denotes an alkali metal ion or hydrogen ion or a glycerin residue orsugar residue, and X is selected from the group consisting of aninorganic or organic counter ion, provided that when L is selected fromthe group consisting of ##STR52## X⁻ does not exist.
 13. The compositionas claimed in claim 12, in which a mold ratio of (a) to (b) ranges from99.9/0.1 to 20/80.
 14. The composition as claimed in claim 12, whichfurther contains one or more agents selected from the group consistingof a surfactant, a divalent metal ion sequestering agent, an alkalineagent, an inorganic electrolyte, an anti-redeposition agent, an enzyme,a fluorescent whitening agent, a stabilizer for the peroxide, a perfumeand a coloring agent.
 15. A bleaching composition which comprises (a) aperoxygen compound capable of yielding hydrogen peroxide in an aqueoussolution and (b) an organic peracid precursor having the formula (I):##STR53## where R₁ is selected from the group consisting of astraight-chain or branched-chain C₁ -C₂₀ alkyl or alkenyl group whichmay have a substituent group, and an unsubstituted or C₁ -C₂₀alkyl-substituted aryl group, X is ##STR54## Y is R₅ R₂ and R₃ each isselected from the group consisting of a C₁ -C₃ alkyl group which mayhave a substituent group,R₄ and R₅ each is selected from the groupconsisting of a C₁ -C₁₂ alkylene group which may have a substituentgroup, ##STR55## L is a leaving group selected from the group consistingof ##STR56## where R₆ and R₉ each is an alkyl group, R₇ and R₈ each isselected from the group consisting of hydrogen or an alkyl group, and M⁺denotes an alkali metal ion or hydrogen ion or a glycerin residue orsugar residue, and X is selected from the group consisting of aninorganic or organic counter ion, provided that when L is selected fromthe group consisting of ##STR57## X⁻ does not exist.
 16. The compositionas claimed in claim 15, in which a mold ratio of (a) to (b) ranges from99.9/0.1 to 20/80.
 17. The composition as claimed in claim 15, whichfurther contains one or more agents selected from the group consistingof a surfactant, a divalent metal ion sequestering agent, an alkalineagent, an inorganic electrolyte, an anti-redeposition agent, an enzyme,a fluorescent whitening agent, a stabilizer for the peroxide, a perfumeand a coloring agent.